Composition For High Performance Glass High Performance Glass Fibers And Articles Therefrom

ABSTRACT

Glass batch compositions for the formation of high-modulus, and high-strength glass fibers as well as fibers suitable for use as textile and reinforcements are disclosed. Fibers formed of the composition are especially suitable for use in high-strength, low-weight applications such as windmill blades and high strength and modulus applications where strength and stiffness are required in the composite. The glass composition is up to about 70.5 weight % SiO 2 , about 24.5 weight % Al 2 O 3 , about 22 weight % alkaline earth oxides and may include small amounts of alkali metal oxides and ZrO 2 . Fiberglass-reinforced composite articles such as windmill blades are also disclosed.

TECHNICAL FIELD AND INDUSTRIAL APPLICABILITY OF THE INVENTION

The present invention is generally directed to a composition for continuous glass fibers for use in high-strength applications as well as high-strength glass fibers and articles.

BACKGROUND OF THE INVENTION

The most common glass composition for making continuous glass fiber strands is “E-Glass.” The liquidus temperature of E-Glass is approximately 2100° F. (1149° C.) or lower. One advantage of E-Glass is that its liquidus temperature allows operating temperatures for producing glass fibers to be approximately 1900° F. to 2400° F. (1038° C. to 1316° C.). The ASTM classification for E-glass fiber yarns used in printed circuit boards and aerospace applications defines the composition to be 52 to 56 weight % SiO₂, 16 to 25 weight % CaO, 12 to 16 weight % Al₂O₃, 5 to 10 weight % B₂O₃, 0 to 5 weight % MgO, 0 to 2 weight % Na₂O and K₂O, 0 to 0.8 weight % TiO₂, 0.05 to 0.4 weight % Fe₂O₃ and 0 to 1.0 weight % Fluorine.

Boron-free fibers are sold under the trademark ADVANTEX (Owens Corning, Toledo, Ohio, USA). Boron-Free fibers, such as are disclosed in U.S. Pat. No. 5,789,329, incorporated herein by reference in its entirety, offer a significant improvement in operating temperatures over boron-containing E-glass. Boron-Free glass fibers fall under the ASTM definition for E-glass fibers for use in general-use applications.

S-Glass is a family of glasses composed primarily of the oxides of magnesium, aluminum, and silicon with a chemical composition that produces glass fibers having a higher mechanical strength than E-Glass fibers. The composition for forming S-Glass includes approximately 65 weight % SiO₂, 25 weight % Al₂O₃, and 10 weight % MgO. S-glass has a composition that was originally designed to be used in high-strength applications such as ballistic armor.

R-Glass is a family of glasses that are composed primarily of the oxides of silicon, aluminum, magnesium, and calcium with a chemical composition that produces glass fibers with a higher mechanical strength than E-Glass fibers. R-Glass has a composition that contains about 58 to about 60 weight % SiO₂, about 23.5 to about 25.5 weight % Al₂O₃, about 14 to about 17 weight % CaO plus MgO, 0% B₂O₃, 0% F₂ and less than about 2 weight % of miscellaneous components. R-Glass contains more alumina and silica than E-Glass and requires higher melting and processing temperatures during fiber forming. Typically, the melting and processing temperatures for R-Glass are at least about 160° C. higher than those for E-Glass. This increase in processing temperature requires the use of a high-cost platinum-lined melter. In addition, the close proximity of the liquidus temperature to the forming temperature in R-Glass requires that the glass be fiberized at a viscosity lower than E-Glass, which is customarily fiberized at or near about 1000 poise. Fiberizing R-Glass at the customary 1000 poise viscosity would likely result in glass devitrification, which causes process interruptions and reduced productivity.

Tables IA-IE set forth the compositions for a number of conventional high-strength glass compositions.

TABLE I-A RUSSIAN CONTINUOUS Chinese ROVING NITTOBO NITTOBO High MAGNESIUM ″T″ ″T″ Strength ALUMINO- Glass Fabric Glass Fabric Constituent glass SILICATE ″B″ (Yarn) ″C″ SiO₂ 55.08 55.81 64.58 64.64 CaO 0.33 0.38 0.44 0.40 Al₂O₃ 25.22 23.78 24.44 24.57 B₂O₃ 1.85 0.03 0.03 MgO 15.96 15.08 9.95 9.92 Na₂O 0.12 0.063 0.08 0.09 Fluorine 0.03 0.034 0.037 TiO₂ 0.023 2.33 0.019 0.018 Fe₂O₃ 1.1 0.388 0.187 0.180 K₂O 0.039 0.56 0.007 0.010 ZrO₂ 0.007 0.15 Cr₂O₃ 0.011 0.003 0.003 Li₂O 1.63 CeO₂

TABLE I-B Nitto Nitto Vetrotex Saint Boseki Boseki Nitto Boseki TE Gobain SR Glass Polotsk A&P NT6030 Glass RST- Stratifils SR CG STEKLOVOLOKNO Constituent Yarn Yarn 220PA-535CS 250 P109 High Strength Glass SiO₂ 65.51 64.60 64.20 63.90 58.64 CaO 0.44 0.58 0.63 0.26 0.61 Al₂O₃ 24.06 24.60 25.10 24.40 25.41 B₂O₃ 0.04 MgO 9.73 9.90 9.90 10.00 14.18 Na₂O 0.04 0.06 0.020 0.039 0.05 Fluorine 0.07 0.02 TiO₂ 0.016 0.000 0.000 0.210 0.624 Fe₂O₃ 0.067 0.079 0.083 0.520 0.253 K₂O 0.020 0.020 0.020 0.540 0.35 ZrO₂ 0.079 Cr₂O₃ 0.0010 0.001 0.023 Li₂O CeO₂

TABLE I-C Chinese Chinese High High Strength Strength Zentron SOLAIS Advanced Yarn Glass S-2 Glass Glass Glass Yarns Constituent (8 micron) Roving Roving Sample R Glass SiO₂ 55.22 55.49 64.74 64.81 58.46 CaO 0.73 0.29 0.14 0.55 9.39 Al₂O₃ 24.42 24.88 24.70 24.51 24.55 B₂O₃ 3.46 3.52 0.02 0.04 MgO 12.46 12.28 10.24 9.35 5.91 Na₂O 0.104 0.06 0.17 0.16 0.079 Fluorine 0.07 0.02 0.054 TiO₂ 0.32 0.36 0.015 0.04 0.196 Fe₂O₃ 0.980 0.930 0.045 0.238 0.400 K₂O 0.240 0.150 0.005 0.03 0.67 ZrO₂ Cr₂O₃ 0.0050 0.007 0.005 Li₂O 0.59 0.63 CeO₂ 1.23 1.25

TABLE I-D IVG Advanced IVG IVG Vertex Glass Vertex Vertex Outside Yarns Culimeta B96 675 Glass #1 Glass Constituent S Glass Roving Yarn Roving Roving SiO₂ 64.61 59.37 58.34 58.58 58.12 CaO 0.17 0.27 0.31 0.30 0.31 Al₂O₃ 24.84 25.49 23.81 24.26 24.09 B₂O₃ 0.04 0.05 MgO 10.11 13.47 14.99 15.02 15.36 Na₂O 0.118 0.024 0.05 0.02 0.03 Fluorine 0.03 0.04 0.04 0.04 TiO₂ 0.011 0.530 1.380 0.67 0.91 Fe₂O₃ 0.042 0.374 0.333 0.336 0.303 K₂O 0.48 0.42 0.28 0.29 ZrO₂ 0.152 0.129 0.165 0.157 Cr₂O₃ 0.0050 0.0120 0.0100 0.0120 0.0120 Li₂O CeO₂

TABLE I-E IVG Vertex RH CG250 Outside #2 P109 Glass Constituent Glass Roving Fiber Strand SiO₂ 58.69 58.54 CaO 0.29 9.35 Al₂O₃ 24.3 25.39 B₂O₃ MgO 15.06 6.15 Na₂O 0.03 0.10 Fluorine 0.04 0.16 TiO₂ 0.64 0.008 Fe₂O₃ 0.331 0.069 K₂O 0.36 0.14 ZrO₂ 0.187 0.006 Cr₂O₃ 0.0130 Li₂O CeO₂

R-Glass and S-Glass are produced by melting the constituents of the compositions in a platinum-lined melting container. The costs of forming R-Glass and S-Glass fibers are dramatically higher than E-Glass fibers due to the cost of producing the fibers in such melters. Thus, there is a need in the art for glass compositions useful in the formation of high performance glass fibers from a direct-melt process in a refractory-lined furnace and fibers formed from such compositions.

SUMMARY OF THE INVENTION

The invention, in part, is a glass composition for the formation of continuous glass fibers that are suitable for use in high-strength applications. The composition of the present invention may be inexpensively formed into glass fibers using low-cost, direct melting in refractory-lined furnaces due to the relatively low fiberizing temperature of the glass fibers. Once formed into fibers, the glass composition provides the strength characteristics of higher-priced glass fibers such as S-Glass. The composition of the present invention includes about 60.5 to about 70.5 weight % SiO₂, about 10.0 to about 24.5 weight % Al₂O₃, about 6.0 to about 20.0 weight % RO, where RO equals the sum of MgO, CaO, SrO and BaO, and about 0.0 to about 3.0 weight % alkali metal oxides. In a preferred embodiment, the glass composition is composed of about 61 to about 68 weight % SiO₂, about 15 to about 19 weight % Al₂O₃, about 15 to about 20 weight % RO, where RO equals the sum of MgO, CaO, SrO and BaO, and about 0 to about 3 weight % alkali metal oxides. The composition preferably does not contain more than about 4 weight % of oxides or halogens selected from the group consisting of ZnO, SO₃, Fluorine, B₂O₃, TiO₂, ZrO₂ and Fe₂O₃. The desired properties of the glass composition of the present invention include a fiberizing temperature of less than about 2650° F. and a liquidus temperature that is preferably below the fiberizing temperature by at least about 80° F., more preferably by at least about 120° F., and most preferably by at least about 150° F.

DETAILED DESCRIPTION AND PREFERRED EMBODIMENTS OF THE INVENTION

Fiberizing properties of the glass composition of the present invention include the fiberizing temperature, the liquidus, and delta-T. The fiberizing temperature is defined as the temperature that corresponds to a viscosity of about 1000 Poise. As discussed in more detail below, a lowered fiberizing temperature reduces the production cost of the fibers, allows for a longer bushing life, increases throughput, permits the glass to be melted in a refractory-lined melter, and reduces energy usage. For example, at a lower fiberizing temperature, a bushing operates at a cooler temperature and does not “sag” as quickly. Sag is a phenomenon that occurs in bushings that are held at an elevated temperature for extended periods of time. By lowering the fiberizing temperature, the sag rate of the bushing may be reduced and the bushing life can be increased. In addition, a lower fiberizing temperature allows for a higher throughput since more glass can be melted in a given period at a given energy input. As a result, production cost is reduced. In addition, a lower fiberizing temperature will also permit glass formed with the inventive composition to be melted in a refractory-lined melter since both its melting and fiberizing temperatures are below the upper use temperatures of many commercially available refractories.

The liquidus is defined as the highest temperature at which equilibrium exists between liquid glass and its primary crystalline phase. At all temperatures above the liquidus, the glass is free from crystals in its primary phase. At temperatures below the liquidus, crystals may form.

Another fiberizing property is delta-T (ΔT), which is defined as the difference between the fiberizing temperature and the liquidus. A larger ΔT offers a greater degree of flexibility during the formation of the glass fibers and helps to inhibit devitrification of the glass (that is, the formation of crystals within the melt) during melting and fiberizing. Increasing the ΔT also reduces the production cost of the glass fibers by allowing for a greater bushing life and by providing a wider process window for forming fibers.

The glasses of the present invention are suitable for melting in traditional commercially available refractory-lined glass melters, which are widely used in the manufacture of glass reinforcement fibers. Starting batch components typically include SiO₂ (ground silica sand), and Al₂O₃ (calcined alumina), as well as chain modifiers from source materials such as MgCO₃ (magnesite), CaCO₃ (limestone), SrCO₃ (strontianite), BaCO₃ (witherite), ZrSiO₄ (zircon), and Na₂CO₃ (natrite).

The glass batch is preferably composed of about 60.5 to about 70.5 weight percent SiO₂, about 10.0 to about 24.5 weight percent Al₂O₃, about 6.0 to about 20.0 weight percent RO, where RO equals the sum of MgO, CaO, and SrO, and about 0.0 to about 3.0 weight percent alkali metal oxides. A fiber formed in accordance with the present invention will typically include small amounts of ZnO, SO₃, Fluorine, B₂O₃, TiO₂ and Fe₂O₃, preferably in an amount of less than 4 weight percent. In addition, a fiber formed in accordance with the present invention will preferably having a fiberizing temperature of less than about 2650° F., a ΔT of at least about 80° F., preferably a ΔT of at least about 120° F., and most preferably a ΔT of at least 150° F., and a coefficient of thermal expansion (CTE) of about 2.28×10⁻⁶ in/in/° F. to about 2.77×10⁻⁶ in/in/° F. Further, the glass of the present invention preferably have a strength in excess of 600 KPSI, preferably a strength in excess of about 630 KPSI, and most preferably a strength in excess of about 695 KPSI. Further, the glass fibers will desirably have a modulus greater than about 12.0 MPSI, preferably greater then about 12.18 MPSI, and most preferably greater then about 12.6 MPSI. It will be appreciated that certain details of construction are not provided in view of such details being conventional and well within the skill of the art.

The present invention also includes a composite material including glass fibers, as described above, in combination with a hardenable matrix material. The composite material is especially useful in applications where high strength and stiffness and low weight are desired. Such applications include aircraft, automotive, and wind energy (such as windmill blades) as well as any other application where low weight, stiffness and high strength are desired. Suitable hardenable matrix materials include thermoset and thermoplastic resins. By way of example, suitable thermoset matrix materials include vinyl esters, polyesters, resin epoxies and combinations or copolymers thereof. Typically, windmill blades are formed by any suitable composite fabrication technique, such as vacuum-assisted resin infusion or pre-impregnated reinforcement lay-up.

Having generally described this invention, a further understanding can be obtained by reference to certain specific examples illustrated below which are provided for purposes of illustration only and are not intended to be all inclusive or limiting unless otherwise specified.

EXAMPLES

The glasses in the examples listed in Tables IIA-IIC were melted in platinum crucibles or in a continuous platinum-lined melter for determining the mechanical and physical properties of the glass and fibers produced therefrom. The units of measurement for the physical properties are: Viscosity (° F.), Liquidus temperature (° F.) and ΔT (° F.). In some examples the glasses were fiberized and Strength (KPsi), Density (g/cc), Modulus (MPsi), Softening Point (° F.) and coefficient of thermal expansion (CTE) (in/in/(° F.)) were measured.

The fiberizing temperature was measured using a rotating spindle viscometer. The fiberizing viscosity is defined as 1000 Poise. The liquidus was measured by placing a platinum container filled with glass in a thermal gradient furnace for 16 hours. The greatest temperature at which crystals were present was considered the liquidus temperature. The modulus was measured using the sonic technique on a single fiber of glass. The tensile strength was measured on a pristine single fiber. The CTE was measured with a dilatometer over the range of temperature from 25 to 600 degrees C. The softening point temperature was measured using the ASTM C338 fiber-elongation method.

TABLE IIA Glass Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 SiO₂ 62.63 62.42 61.75 63.01 63.07 63.16 CaO 8.49 8.64 8.57 4.84 4.85 4.8 Al₂O₃ 18.50 18.54 18.82 19.99 20.03 19.76 MgO 9.47 9.64 9.65 11.26 11.28 11.33 Na₂O 0.70 0.69 0.70 0.70 TiO₂ 0.00 0.01 0.01 0.00 0.01 0.02 Fe₂O₃ 0.20 0.05 0.045 0.20 0.05 0.037 Measured Viscosity (° F.) 2491 na na 2514 na na Measured Liquidus (° F.) 2261 2247 na 2335 na na Measured DT (° F.) 230 na na 179 na na Measured Strength (KPsi) 672 na na 695 na na Measured Density (g/cc) 2.556 na na 2.530 na na Measured Modulus (MPsi) 12.4 12.6 na 12.6 12.7 na Softening Point (° F.) na na na 1765 na na CTE in/in/(° F.) na na na 2.28 × 10⁻⁶ na na

TABLE II-B Glass Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 SiO₂ 62.32 63.89 63.14 61.39 61.39 65.00 CaO 11.56 11.21 11.96 11.96 8.71 13.00 Al₂O₃ 17.25 16.39 16.39 18.14 18.89 15.00 MgO 7.98 6.62 6.62 6.62 9.62 5.00 Na₂O 0.70 0.75 0.75 0.75 0.25 1.00 TiO₂ 0.00 0.75 0.75 0.75 0.75 1.00 Fe₂O₃ 0.20 0.39 0.39 0.39 0.39 Measured 2458 2493 2435 2431 2434 2509 Viscosity (° F.) Measured 2301 2268 2294 2353 2261 2226 Liquidus (° F.) Measured DT 157 225 141 78 173 283 (° F.) Measured 632 636 622 615 682 612 Strength (KPsi) Measured 2.573 2.553 2.567 2.567 2.564 na Density (g/cc) Measured 12.2 12.2 12.2 12.2 12.6 na Modulus (MPsi) Softening Point 1729 na na na na na (° F.) CTE in/in/(° F.) 2.77 × 10⁻⁶ na na na na na

TABLE II-C Glass Ex. 13 Ex. 14 Ex. 15 Ex. 16 Ex. 17 Ex. 18 SiO₂ 63.89 65.00 64.00 63.89 65.00 65.00 CaO 6.96 14.00 4.00 8.96 14.00 12.50 Al₂O₃ 18.64 15.00 20.00 18.89 15.00 15.00 MgO 9.62 6.00 11.00 6.62 5.00 5.00 Na₂O 0.25 0.00 1.00 0.75 0.00 1.00 TiO₂ 0.25 0.00 0.00 0.75 1.00 1.00 Fe₂O₃ 0.39 0.00 0.00 0.14 0.00 0.50 Measured Viscosity (° F.) 2513 2508 2548 2565 2481 2523 Measured Liquidus (° F.) 2337 2373 2401 2288 2403 2227 Measured DT (° F.) 176 135 147 277 78 296 Measured Strength (KPsi) 695 624 na na 604 na Measured Density (g/cc) 2.480 2.554 na na 2.546 na Measured Modulus (MPsi) 12.3 12.0 na na 11.9 na Softening Point (° F.) na na na na na na CTE in/in/(° F.) na na na na na na

As is understood in the art, the above exemplary inventive compositions do not always total 100% of the listed components due to statistical conventions (such as, rounding and averaging) and the fact that some compositions may include impurities that are not listed. Of course, the actual amounts of all components, including any impurities, in a composition always total 100%. Furthermore, it should be understood that where small quantities of components are specified in the compositions, for example, quantities on the order of about 0.05 weight percent or less, those components may be present in the form of trace impurities present in the raw materials, rather than intentionally added.

Additionally, components may be added to the batch composition, for example, to facilitate processing, that are later eliminated, thereby forming a glass composition that is essentially free of such components. Thus, for instance, minute quantities of components such as fluorine and sulfate may be present as trace impurities in the raw materials providing the silica, calcia, alumina, and magnesia components in commercial practice of the invention or they may be processing aids that are essentially removed during manufacture.

As apparent from the above examples, glass fiber compositions of the invention have advantageous properties, such as low fiberizing temperatures and wide differences between the liquidus temperatures and the fiberizing temperatures (high ΔT values). Other advantages and obvious modifications of the invention will be apparent to the artisan from the above description and further through practice of the invention). The high-performance glass of the present invention melts and refines at relatively low temperatures, has a workable viscosity over a wide range of relatively low temperatures, and a low liquidus temperature range.

The invention of this application has been described above both generically and with regard to specific embodiments. Although the invention has been set forth in what is believed to be the preferred embodiments, a wide variety of alternatives known to those of skill in the art can be selected within the generic disclosure. Other advantages and obvious modifications of the invention will be apparent to the artisan from the above description and further through practice of the invention. The invention is not otherwise limited, except for the recitation of the claims set forth below. 

1.-20. (canceled)
 21. A glass fiber formed from a batch composition, said batch composition comprising: about 60.5 to about 70.5 weight percent SiO₂; about 10 to about 24.5 weight percent Al₂O₃; about 6 to about 20 weight percent alkaline earth oxide, said alkaline earth oxide being the sum of MgO, CaO, SrO and BaO; and 0 to about 3 weight percent alkali metal oxide;
 22. The glass fiber of claim 21, further comprising less than 4 weight percent of compounds selected from the group consisting of ZnO, SO₃, Fluorine, B₂O₃, TiO₂ and Fe₂O₃.
 23. The glass fiber of claim 21, wherein 5 to 11.33 weight percent of said alkaline earth oxide is MgO.
 24. The glass fiber of claim 21, wherein from 4.0 to 14.0 weight percent of said alkaline earth oxide is CaO.
 25. The glass fiber of claim 21, wherein said glass has a fiberizing temperature of less than about 2650° F., and a ΔT at least about 80° F.
 26. The glass fiber of claim 25, wherein the ΔT for the glass is at least about 120° F.
 27. The glass fiber of claim 25 wherein the ΔT for the glass is at least about 150° F.
 28. The glass fiber of claim 21, wherein said fiber has a coefficient of thermal expansion (CTE) between about 2.28×10⁻⁶ in/in/° F. and about 2.77×10⁻⁶ in/in/° F.
 29. The glass fiber of claim 21, wherein said fiber has a strength in excess of about 600 KPSI.
 30. The glass fiber of claim 21, wherein said fiber has a strength in excess of about 630 KPSI.
 31. The glass fiber of claim 21, wherein said fiber has a strength in excess of about 695 KPSI.
 32. The glass fiber of claim 21, wherein said fiber has a modulus in excess of about 12.0 MPSI
 33. The glass fiber of claim 21, wherein said fiber has a modulus in excess of about 12.2 MPSI
 34. The glass fiber of claim 21, wherein said fiber has a modulus in excess of about 12.6 MPSI.
 35. A fiberglass reinforced article comprising: glass fibers comprising: about 60.5 to about 70.5 weight percent SiO₂; about 10 to about 24.5 weight percent Al₂O₃; about 6.0 to about 20.0 weight percent alkaline earth oxide, said alkaline earth oxide being the sum of MgO, CaO, SrO and BaO; and up to 3 weight percent alkali metal oxides; and a curable matrix material,
 36. The fiberglass reinforced article of claim 35, wherein 5 to 11.33 weight percent of said alkaline earth oxide is MgO and from 4.0 to 14.0 weight percent of said alkaline earth oxide is CaO.
 37. The fiberglass reinforced article of claim 35, wherein said reinforced article is a blade for a wind turbine.
 38. The fiberglass reinforced article of claim 35, wherein said curable matrix material is selected from the group consisting of vinyl ester, polyester, resin epoxy and combinations or copolymers thereof.
 39. The fiberglass reinforced article of claim 35, wherein said glass fibers further comprise less than 4 weight percent of compounds selected from the group consisting of ZnO, SO₃, Fluorine, B₂O₃, TiO₂ and Fe₂O₃.
 40. A glass fiber formed from a batch composition, said batch comprising: about 60.5 to about 70.5 weight percent SiO₂; about 10 to about 24.5 weight percent Al₂O₃; about 6 to about 20 weight percent alkaline earth oxide, 5 to 11.33 weight percent of said alkaline earth oxide being MgO and 4 to 14 weight percent of said alkaline earth oxide being CaO; and about 0 to about 3 weight percent alkali metal oxide.
 41. The glass fiber of claim 40, further comprising less than 4 weight percent of compounds selected from the group consisting of ZnO, SO₃, Fluorine, B₂O₃, TiO₂ and Fe₂O₃.
 42. The glass fiber of claim 40, wherein said glass has a fiberizing temperature of less than about 2650° F. and a ΔT at least about 80° F.
 43. A fiberglass reinforced article comprising: glass fibers comprising: about 60.5 to about 70.5 weight percent SiO₂; about 10 to about 24.5 weight percent Al₂O₃; about 6.0 to about 20.0 weight percent alkaline earth oxide, 5 to 11.33 weight percent of said alkaline earth oxide being MgO and from 4.0 to 14.0 weight percent of said alkaline earth oxide being CaO; 0 to about 3 weight percent alkali metal oxides; and less than 4 weight percent of compounds selected from the group consisting of ZnO, SO₃, Fluorine, B₂O₃, TiO₂ and Fe₂O₃; and a curable matrix material.
 44. The fiberglass reinforced article of claim 43, wherein said glass has a fiberizing temperature of less than about 2650° F. and a ΔT at least about 80° F. 